The present invention relates to a silver halide color photographic light-sensitive material.
The present invention particularly relates to a silver halide color photographic light-sensitive material that excels in both rapid processing suitability and shading representation at the high density portion of an image obtained by a scanning exposure, and that is also suitable for a conventional xe2x80x9csurfacexe2x80x9d exposure (a conventional flooding exposure).
The present invention also relates to a silver halide color photographic light-sensitive material that excels in rapid processing suitability; that restrains the change in color balance at the peripheral portion of a color photograph, and also provides high maximum colored density, upon a scanning exposure; and that is suitable for a surface exposure.
Current widespread color photographs have become more rapidly and readily available by the improvement of light-sensitive materials and the progress of development processing technique. Particularly in the field of color printing, production of color photographs has been made in accordance with various ends, in lieu of such development as a centralization processing system, owing to production facilities having both a high-speed printer, for mass production, and a large-sized processing apparatus, or the like, which are called xe2x80x9ccolor labs,xe2x80x9d and a dispersion processing system using a small-sized printer processor, which is called a xe2x80x9cminilabxe2x80x9d and is located in the front of a shop.
As to rapid processing, U.S. Pat. No. 4,840,878 discloses a technique of processing a color photographic light-sensitive material comprising a silver halide emulsion having a high silver chloride content, with a color-developing solution containing substantially neither sulfite ion nor benzyl alcohol. Actually, such a light-sensitive material comprising a silver halide emulsion having a high silver chloride content, and a processing method thereof according to the above-described technique, have been put to practical use. Consequently, color prints have become more rapidly and readily available.
Recently, in addition to printing by a conventional surface exposure, it has been practiced to provide a color print obtained from digital image data by reading a negative or positive image with a scanner. Digitalization of an image enables correction, such as gradation retouching, dodging (a shutting light method), and letter-printing at the time of producing a postcard, on the monitor of a computer, without preparing a lith film, and therefore digitalization contributes to improving both the productivity and quality of a color print. Further, digitalization of an image enables receiving image data via the Internet, and producing a color print using the same. The foregoing method is considered to become generalized in the future. In order to obtain a color print from digital image data, use can be made of various kinds of a scanning exposure apparatus of the type in which one pixel by one pixel is subjected to a scanning exposure to light from a light source, such as a cathode ray (CRT) and a laser, in place of a surface exposure through an ordinary negative film.
As mentioned above, as to technique to prepare a color print, printings by both conventional surface exposure and scanning exposure have been practiced, and color print materials for each exclusive use have been put to practical use. Therefore, at the site of color print preparation, two kinds of color print materials are necessary. However, if these different printing techniques could be handled with only a single kind of printing material, it would be convenient. As a result, it is desired to provide a color print material having both surface exposure and scanning exposure suitability.
As to a light-sensitive material having both surface exposure and scanning exposure suitability, U.S. Pat. No. 5,869,228 discloses a technique in which iron ions are locally contained in the surface region of high silver chloride emulsion grains, and further an o-hydroquinone-series compound or p-hydroquinone-series compound is incorporated in a light-sensitive material, whereby photographic properties obtained by a scanning exposure becomes equal to those obtained by a surface exposure. The present inventor studied the light-sensitive material manufactured by applying the foregoing technique. As a result, it was found that, with respect to a color print obtained by a scanning exposure, the problem arose that the shading at the high density portion became unnaturally great. It is possible to correct only the digital data of the shading portion, since the scanning exposure data are digitalized. However, the correction takes so much time and labor that ordinary color labs cannot accept it, in actual fact. Further, as to the light-sensitive material manufactured by applying the technique of the above-mentioned U.S. Pat. No. 5,869,228, it was found that, with respect to a color print obtained by a scanning exposure, another problem arose that the change in color balance became larger at the peripheral portion {for example, as to a one-sixth size (20.3 cmxc3x9725.4 cm), a region of from the end up to about 5 cm}. It is possible to restrain the change in color balance by correcting only digital data at the peripheral portion, since the scanning exposure data are digitalized. However, because the degree of change in color balance differs from one scanning exposure apparatus to another, correction is necessary for each apparatus, and this takes much time and labor. Therefore, the correction of digital data was difficult, in actual fact.
Accordingly, an object of the present invention is to provide a silver halide color photographic light-sensitive material that excels in both rapid processing suitability and shading representation at the high density portion of an image in a color print obtained by a scanning exposure, and that is also suitable for a conventional surface exposure.
Another object of the present invention is to provide a silver halide color photographic light-sensitive material that excels in rapid processing suitability; that restrains the change in color balance at the peripheral portion of a color photograph, and also provides high maximum colored density, upon a scanning exposure; and that is also suitable for a surface exposure.
Other and further objects, features, and advantages of the invention will appear more fully from the following description.
As a result of an intensive study, the present inventor has found that the above-described objects of the present invention can be accomplished by the following means:
(1) A silver halide color photographic light-sensitive material, comprising at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, at least one green-sensitive silver halide emulsion layer containing a magenta coupler, and at least one red-sensitive silver halide emulsion layer containing a cyan coupler, provided on a support,
wherein at least one layer of said light-sensitive silver halide emulsion layers contains a silver halide emulsion comprising silver halide grains having a silver chloride content of 95 mol % or more, and
wherein, with respect to each of characteristic curves obtained by a color development of said light-sensitive material after exposure, the following relationship is satisfied:
0.65xe2x89xa6D1xe2x80x2/D1xe2x89xa60.85 
1.1xe2x89xa6log(E2/E1)xe2x89xa61.4
wherein D1 represents a density obtained by exposing to light in an exposure amount-ten times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by a 10xe2x88x921-sec exposure,
D1xe2x80x2 represents a density obtained by exposing to light in an exposure amount ten times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by a 10xe2x88x924-sec exposure,
E1 represents an exposure amount required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by a 10xe2x88x924-sec exposure, and
E2 represents, in the characteristic curve obtained by a 10xe2x88x924-sec exposure, an exposure amount required to provide the density 0.92 times the maximum density in the characteristic curve obtained by a 10xe2x88x921-sec exposure.
(2) The silver halide color photographic light-sensitive material as described in the above item (1), wherein the relationship defined in the item (1), is satisfied in the characteristic curve obtained by a color development of said light-sensitive material after exposure to red light.
(3) The silver halide color photographic light-sensitive material as described in the above item (1) or (2), wherein said emulsion comprises silver halide grains having a silver chloride content of 95 mole % or more and doped with at least two kinds of complexes of metal of the group VIII in the periodic table. (Hereinafter, the silver halide color photographic light-sensitive materials described in the above (1) to (3) are referred to as the first embodiment of the present invention.)
(4) A silver halide color photographic light-sensitive material, comprising at least one blue-sensitive silver halide emulsion layer containing a yellow coupler, at least one green-sensitive silver halide emulsion layer containing a magenta coupler, and at least one red-sensitive silver halide emulsion layer containing a cyan coupler, provided on a support,
wherein at least one layer of said light-sensitive silver halide emulsion layers contains a silver halide emulsion comprising silver halide grains having a silver chloride content of 95 mol % or more, and
wherein, with respect to each of characteristic curves obtained by a color development of said light-sensitive material after exposure, the following relationship is satisfied:
0.65xe2x89xa6D1xe2x80x2/D1xe2x89xa60.85 
0.90xe2x89xa6D1xe2x80x3/D1xe2x80x2xe2x89xa61.00 
0.90xe2x89xa6D2xe2x80x2/D2xe2x89xa61.00 
0.90xe2x89xa6D2xe2x80x3/D2xe2x80x2xe2x89xa61.00 
wherein D1 represents a density obtained by exposing to light in an exposure amount ten times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by a 10xe2x88x921-sec exposure,
D1xe2x80x2 represents a density obtained by exposing to light in an exposure amount ten times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by a 10xe2x88x924-sec exposure,
D1xe2x80x3 represents a density obtained by exposing to light in an exposure amount ten times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by a 10xe2x88x926-sec exposure,
D2 represents a density obtained by exposing to light in an exposure amount thirty times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by a 10xe2x88x921-sec exposure,
D2xe2x80x2 represents a density obtained by exposing to light in an exposure amount thirty times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by a 10xe2x88x924-sec exposure, and
D2xe2x80x3 represents a density obtained by exposing to light in an exposure amount thirty times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by a 10xe2x88x926-sec exposure.
(5) The silver halide color photographic light-sensitive material as described in the above item (4), wherein the relationship defined in the above item (4) is satisfied for a characteristic curve obtained by a color development of said light-sensitive material after exposure to a red light.
(6) The silver halide color photographic light-sensitive material as described in the above item (4) or (5), wherein at least one layer of said light-sensitive silver halide emulsion layers contains silver halide grains having a silver chloride content of 95 mol % or more, and doped with at least two kinds of complexes of metal of the group VIII in the periodic table, in the molar amounts of the complexes to be doped so as to become different from each other by twenty times or more.
(Hereinbelow, the silver halide color photographic light-sensitive materials described in the above (4) to (6) are referred to as the second embodiment of the present invention.)
Herein, the present invention means to include both the first embodiment and the second embodiment, unless otherwise specified.
The present invention will be explained in more detail below.
The silver halide color photographic light-sensitive material of the present invention is defined by the characteristics relating to each of characteristic curves obtained by the following method:
A light-sensitive material is subjected to a gradation exposure for sensitometry using a blue, green or red light, followed by color-development processing. Colored densities thus obtained are measured, to obtain each characteristic curve corresponding to the blue, green or red light. Further, by changing the above-mentioned exposure time to 10xe2x88x921 sec, 10xe2x88x924 sec, and 10xe2x88x926 sec, characteristic curves corresponding to the 10xe2x88x921 sec, 104 sec, and 10xe2x88x926 sec can be obtained. The light-sensitive material of the present invention needs to satisfy the following relationship (1) and/or (2), for any one of the thus-obtained characteristic curves corresponding to a blue, green or red light. It is preferred to satisfy the following relationship (1) and/or (2) for the characteristic curve corresponding to a red light.
Relationship (1)
0.65xe2x89xa6D1xe2x80x2/D1xe2x89xa60.85 
1.1xe2x89xa6log(E2/E1)xe2x89xa61.4 
D1 represents a density obtained by exposing to light in an exposure amount ten times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by exposure for a 10xe2x88x921-sec exposure time,
D1xe2x80x2 represents a density obtained by exposing to light in an exposure amount ten times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by exposure for a 10xe2x88x924-sec exposure time,
E1 represents an exposure amount required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by exposure for a 10xe2x88x924-sec exposure time, and
E2 represents, in the characteristic curve obtained by exposure for a 10xe2x88x924-sec exposure time, an exposure amount required to provide the density 0.92 times the maximum density in the characteristic curve obtained by exposure for a 10xe2x88x921-sec exposure time.
In the case where the log(E2/E1) is less than 1.1, the shading at the high density portion of the image obtained by a scanning exposure becomes unnaturally strong. Further, in the case where the log(E2/E1) is greater than 1.4, the shading at the high density portion of the image obtained by a scanning exposure becomes weak, resulting in an indefinite image (having insufficient depth). On the other hand, in the case where the log(E2/E1) is within the range of 1.1 to 1.4 as defined in the first embodiment of the present invention, depth (conciseness) of the shading at the high density portion of the image obtained by a scanning exposure is excellent. More preferably the log(E2/E1) is in the range of 1.15 to 1.35. In the case where the D1xe2x80x2/D1 is greater than 0.85 or it is less than 0.65, even though the log(E2/E1) is within the range defined in the first embodiment of the present invention, a relation of the shading is of low grade resulting in difficulty in representing a pale shading. Therefore, it is necessary to adjust the D1xe2x80x2/D1 to the range defined in the first embodiment of the present invention. More preferably the D1xe2x80x2/D1 ranges from 0.68 to 0.82.
Relationship (2)
0.65xe2x89xa6D1xe2x80x2/D1xe2x89xa60.85 
0.90xe2x89xa6D1xe2x80x3/D1xe2x80x2xe2x89xa61.00 
0.90xe2x89xa6D2xe2x80x2/D2xe2x89xa61.00 
xe2x80x830.90xe2x89xa6D2xe2x80x3/D2xe2x80x2xe2x89xa61.00
D1 represents a density obtained by exposing to light in an exposure amount ten times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by exposure for a 10xe2x88x921-sec exposure time,
D1xe2x80x2 represents a density obtained by exposing to light in an exposure amount ten times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by exposure for a 10xe2x88x924-sec exposure time,
D1xe2x80x3 represents a density obtained by exposing to light in an exposure amount ten times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by exposure for a 10xe2x88x926-sec exposure time,
D2 represents a density obtained by exposing to light in an exposure amount thirty times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by exposure for a 10xe2x88x921-sec exposure time,
D2xe2x80x2 represents a density obtained by exposing to light in an exposure amount thirty times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by exposure for a 10xe2x88x924-sec exposure time, and
D2xe2x80x3 represents a density obtained by exposing to light in an exposure amount thirty times as much as that required to provide the density of [a density at the unexposed portion+0.02], in the characteristic curve obtained by exposure for a 10xe2x88x926-sec exposure time.
The exposure herein used to obtain the characteristic curve defined by the present invention refers to the above-mentioned xe2x80x9csurfacexe2x80x9d exposure.
If D2xe2x80x2/D2 is less than 0.90, the maximum colored density obtained by a scanning exposure decreases. In the case that D2xe2x80x3/D2xe2x80x2 is less than 0.90, the maximum colored density to be obtained sometimes decrease when some types of scanning exposure apparatus are used. Such a light-sensitive material is not suitable for a wide use. Only in the case that both D2xe2x80x2/D2 and D2xe2x80x3/D2xe2x80x2 each are 0.90 or more, a satisfactory amount of the maximum colored density can be obtained, regardless the type of scanning exposure apparatus. However, in the case that D1xe2x80x2/D1 is less than 0.65 or it is more than 0.85, even though both D2xe2x80x2/D2 and D2xe2x80x3/D2xe2x80x2 are in the ranges defined in the second embodiment of the present invention, such a problem arose that the change in color balance at the peripheral portion of the image obtained by a scanning exposure sometimes became larger. As to the image of a nearly primary color, the change in color balance was hardly observed. However, as to the image of a neutral color balance, i.e., gray, the change in color balance was remarkable. To control D1xe2x80x2/D1in the range of 0.65 to 0.85 enables to restrain the change in color balance at the peripheral portion within an allowable range. In the case that D1xe2x80x3/D1xe2x80x2 is less than 0.90, some types of scanning exposure apparatus sometimes cannot restrain the change in color balance at the peripheral portion within an allowable range. Such a light-sensitive material is not suitable for a wide use. To control D1xe2x80x3/D1xe2x80x2 in the range of 0.90 to 1.00 allows to restrain, within an allowable range, the change in color balance at the peripheral portion of the image obtained by every type of scanning exposure apparatus. D2xe2x80x2/D2 is more preferably in the range of 0.93 to 1.00. D2xe2x80x3/D2xe2x80x2 is more preferably in the range of 0.93 to 1.00. D1xe2x80x2/D1 is more preferably in the range of 0.68 to 0.82. D1xe2x80x2/D1xe2x80x2 is more preferably in the range of 0.93 to 1.00.
In this specification, the exposure defined by only a second (sec.) of exposure time always refers to a surface exposure, unless otherwise specifically mentioned.
As a light source for use in the present invention, there is no particular limitation, so long as they are able to provide a luminous intensity required for each of several exposures. For example, ordinary halogen lamp and mercury lamp may be used. The exposure for obtaining a characteristic curve resulting from an exposure to a light having a specific wavelength, as defined in the present invention, can be carried out using a light of the specific wavelength, which is taken out through a color filter according to an ordinary method. Therefore, the light source per se may contain a light of a wavelength which is sensitive to light-sensitive layers other than a light-sensitive layer which is sensitive to light of the specific wavelength region.
In order to obtain a characteristic curve defined in the present invention, it is preferred to contain two or more kinds of silver halide emulsion having a different photographic speed from each other, in the same silver halide emulsion layer as described above. Using a characteristic curve which is obtained by exposing and color developing a light-sensitive material which comprises a silver halide emulsion layer containing only one kind of the emulsion, an exposure amount (E) required to provide a colored density of 60% of the maximum density obtained by, for example, a 10xe2x88x921-sec exposure, and an exposure amount (Exe2x80x2) required to provide a colored density of 10% of the maximum density obtained by, for example, a 10xe2x88x921-sec exposure are measured. Log(1/E) is defined as a middle density sensitivity, and log(1/Exe2x80x2) as a low density sensitivity. In this case, among two or more kinds of the emulsion contained in the same silver halide emulsion layer, a difference in sensitivity between the highest sensitive emulsion and the lowest sensitive emulsion is preferably in the range of 0.05 to 0.60, more preferably in the range of 0.10 to 0.50, in terms of both the low density sensitivity and the middle density sensitivity resulting from a 10xe2x88x921-sec exposure. Further, it is preferable that a difference in the middle density sensitivity resulting from a 10xe2x88x924-sec exposure is larger by at least 0.05 than a difference in the middle density sensitivity obtained by a 10xe2x88x921-sec exposure. Further, it is more preferable that a difference in the low density sensitivity resulting from a 10xe2x88x924-sec exposure is almost the same (within 0.05) as a difference in the low density sensitivity obtained by a 10xe2x88x921-sec exposure.
Further, as to the relationship of the sensitivities obtained by 10xe2x88x924-sec exposure and 10xe2x88x926-sec exposure, the difference of sensitivities at a 10xe2x88x924-sec exposure and the difference of sensitivities at a 10xe2x88x926-sec exposure, preferably have a difference within 0.05, respectively, in both the difference of middle density sensitivities and the difference of low density sensitivities.
In order to change a photographic speed of the silver halide emulsion, usually the size of silver halide emulsion grains is changed. Generally, a photographic speed can be enhanced by making the grain size larger, or it can be lowered by making the grain size smaller. It is more preferable that each of these silver halide emulsion grains having a different size be mono-dispersed grains.
In order to obtain a silver halide emulsion whose photographic property owing to each exposure time has the characteristics defined by the present invention, it is also preferred to use, in the preparation of the emulsion, the techniques, such as regulation of the amount of a chemical sensitizer, regulation of the chemical sensitization conditions (pAg, pH, temperature, time, etc.), and/or addition of a complex of metal of the group VIII of the periodic table to be contained in the silver halide emulsion and regulation of the amount of the complex, etc., in addition to (in combination with) alteration of the size of silver halide emulsion grains as mentioned above. Among these techniques, more preferred is to use the technique in which a complex of metal of the group VIII of the periodic table is incorporated in a silver halide emulsion in combination with the alteration of the grain size.
For example, in the case where a silver halide emulsion layer contains two kinds of silver halide emulsions each containing both a complex of metal of the group VIII of the periodic table and chemically sensitized silver halide grains having a different grain size from each other, the value of log(E2/E1) can be changed, without a substantial change in the value of D1xe2x80x2/D1, by changing the amount of the complex of metal of the group VIII of the periodic table, which is incorporated in the emulsion having a smaller grain size. On the other hand, by changing the amount of the complex of metal of the group VIII of the periodic table, which is incorporated in the emulsion having a larger grain size, the value of D1xe2x80x2/D1 can be changed without a substantial change in the value of log(E2/E1). Namely, the values of D1xe2x80x2/D1and log(E2/E1) can almost independently be changed by individually altering the amount of the complex of metal of the group VIII of the periodic table, which is incorporated in the silver halide emulsion having a smaller grain size or a larger grain size, respectively.
Further, for example, in the case where a silver halide emulsion layer contains two kinds of silver halide emulsions each containing both a complex of metal of the group VIII of the periodic table and chemically sensitized silver halide grains having a different grain size from each other, the values of both D2xe2x80x2/D2 and D2xe2x80x3/D2xe2x80x2 can be changed corresponding to a variation of the values of both D1xe2x80x2/D1 and D1xe2x80x3/D1xe2x80x2 by changing the amount of the complex of metal of the group VIII of the periodic table, which is incorporated in the emulsion having a smaller grain size. On the other hand, by changing the amount of the complex of metal of the group VIII of the periodic table, which is incorporated in the emulsion having a larger grain size, the values of both D1xe2x80x2/D1 and D1xe2x80x3/D1xe2x80x2 can be changed without a substantial change in the values of both D2xe2x80x2/D2 and D2xe2x80x3/D2xe2x80x2. Namely, the values of D1xe2x80x2/D1, D1xe2x80x3/D1xe2x80x2, D2xe2x80x2/D2 and D2xe2x80x3/D2xe2x80x2 can almost independently be changed by individually altering the amount of the complex of metal of the group VIII of the periodic table, which is incorporated in the silver halide emulsion having a smaller grain size or a larger grain size, respectively.
In the silver halide color light-sensitive material of the present invention, it is preferred to dope silver halide grains with a complex of metal of the group VIII of the periodic table. The metal complex may be incorporated in the silver halide grains at the time of the formation of the silver halide grains, by allowing them to be present in an aqueous solution of gelatin or another protective colloidal polymer as a dispersion medium, an aqueous solution of halide, an aqueous solution of silver salt, or other aqueous solutions. Further, in the case where a silver bromide-localized phase is formed by addition of silver bromide fine grains and/or silver chlorobromide fine grains, the metal complex can also be incorporated selectively in the silver bromide-localized phase by using fine grains which have previously contained the metal complex.
In the present invention, it is preferred to add a complex of metal of the group VIII of the periodic table to the silver halide grain in a light-sensitive silver halide emulsion layer, more preferably in a red-sensitive emulsion layer. Examples of the metal complex include complexes of iron, cobalt, nickel, ruthenium, rhodium, iridium or platinum. Among these, complexes of iron, iridium or ruthenium are preferably used. It is more preferable that a complex of iron or ruthenium be concentrated on the surface layer which is 50% or less of the volume of a silver halide grain so as to become richer than the other portion of the silver halide grain. The term xe2x80x9c50% or less of the volume of a grainxe2x80x9d herein used refers to a surface portion equivalent to 50% or less of the volume of one grain. The surface portion is more preferably 40% or less by volume, furthermore preferably 20% or less by volume. Iridium complex is also preferably contained in the silver bromide rich phase as mentioned above, in addition to the embodiment that it is added at the time of the formation of silver halide grain to contain therein.
Further, it is most preferable that a Group VIII metal complex for use in the present invention be used in combination of two or more kinds thereof rather than a single use. In the case where two or more kinds of Group VIII metal complexes are contained in the same emulsion grain, any two kinds of these metal complexes are preferably contained in a different molar amount from each other. More preferably one complex be contained in the molar amount 20 times or more, most preferably 30 times or more and 10,000 times or less, as much as that of the other, respectively. In the present invention, it is preferred to use complexes of iron and iridium, or complexes of ruthenium and iridium in combination, respectively.
Specific examples of iron, ruthenium and iridium complexes which can be used to incorporate in silver halide grains are shown below. However, the present invention should not be limited to these compounds.
(Iron compounds)
Ferrous arsenate, ferrous bromide, ferrous carbonatexe2x80xa2monohydrate, ferrous chloride, ferrous citrate, ferrous fluoride, ferrous formate, ferrous gluconate, ferrous hydroxide, ferrous iodide, ferrous lactate, ferrous oxalatexe2x80xa2dihydrate, ferrous succinate, ferrous sulfatexe2x80xa2heptahydrate, ferrous thiocyanatexe2x80xa2trihydrate, ferrous nitratexe2x80xa2hexahydrate, ammonium iron (II) nitrate, basic ferric acetate, ferric albuminate, ammonium iron (III) acetate, ferric bromide, ferric chloride, ferric chromate, ferric citrate, ferric fluoride, ferric formate, ferric glycerophosphate, ferric hydroxide, acidic ferric phosphate, ferric nitratexe2x80xa2nonahydrate, ferric phosphate, ferric pyrophosphate, sodium iron (III) pyrophosphate, ferric thiocyanate, ferric sulfatexe2x80xa2nonahydrate, ammonium iron (III) sulfate, guanidinium iron (III) sulfate, ammonium iron (III) citrate, potassium hexacyano ferrate (II)xe2x80xa2trihydrate, potassium pentacyanoammine ferrate (II), sodium ethylenedinitrilotetraacetato ferrate (III), potassium hexacyano ferrate (III).
(Ruthenium Compounds)
Ruthenium (VI) fluoride, ruthenium (IV) chloridexe2x80xa2heptahydrate, potassium hexachlororuthenate (IV), ruthenium (III) chloride, ruthenium (III) bromide, ruthenium (III) iodide, hexaammine ruthenium (III) bromide, chloropentaammine ruthenium (III) chloride, hexaammine ruthenium (II) chloride, potassium hexacyano ruthenate (II)xe2x80xa2trihydrate.
(Iridium Compounds)
Potassium hexachloro iridate (IV), potassium hexabromo iridate (IV), ammonium hexachloro iridate (IV), iridium (III) bromidexe2x80xa2tetrahydrate, iridium (III) iodide, potassium hexachloro iridate (III)xe2x80xa2trihydrate, potassium hexabromo iridate (III), potassium tris(oxarato) iridate (III)xe2x80xa2tetrahydrate, potassium hexacyano iridate (III), iridium (II) chloride.
Of these compounds, particularly preferred are hexacyano ferrate (II) salts, hexacyano ferrate (III) salts, hexacyano ruthenate (II) salts, hexachloro iridate (IV) salts, hexabromo iridate (IV) salts, hexachloro iridate (III) salts, and hexabromo iridate (III) salts.
The amount to be added of these metal ions belonging to the group VIII, though it may change over a wide range in accordance with their intended usage, is preferably 10xe2x88x929 mol to 10xe2x88x923 mol, and more preferably 10xe2x88x928 mol to 5xc3x9710xe2x88x924 mol, per mol of silver halide.
In addition to the metal ions belonging to the group VIII of the periodic table, other metals, such as copper, gold, zinc, cadmium, and lead, may be contained. These metals may be contained together with the metal(s) of the group VIII in the same layer, or they may be contained in a layer free of the metal of group VIII, in accordance with their intended usage. The amount to be added of these metal ions, though it may change over a wide range in accordance with their intended usage, is generally preferably from 10xe2x88x929 mol to 10xe2x88x922 mol per mol of silver halide.
The silver halide emulsion for use in the present invention is generally subjected to chemical sensitization. As to the chemical sensitization method, sulfur sensitization typified by the addition of an unstable sulfur compound, noble metal sensitization typified by gold sensitization, and reduction sensitization may be used independently or in combination. As compounds used for the chemical sensitization, those described in JP-A-62-215272 (xe2x80x9cJP-Axe2x80x9d means unexamined published Japanese patent application), page 18, right lower column to page 22, right upper column are preferably used.
Preferably the silver halide emulsion for use in the present invention is subjected to gold sensitization in a usual manner. In order to carry out gold sensitization, compounds, such as chloroauric acid or a salt thereof, gold thiocyanates and gold thiosulfates, may be used. The amount of these compounds to be added may spread over a wide range corresponding to the occasion. However, the amount is preferably in the range of 5xc3x9710xe2x88x927 mole to 5xc3x9710xe2x88x923 mole, more preferably in the range of 1xc3x9710xe2x88x926 mole to 1xc3x9710xe2x88x924 mole, per mole of silver halide.
In the present invention, gold sensitization may be used in combination with other sensitizing method, for example, sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, or noble metal sensitization using a noble metal other than a gold compound.
In the silver halide color photographic material of the present invention, silver halide grains having a silver chloride content of 95 mole % or more are contained in at least one light-sensitive silver halide emulsion layer. Preferably the silver halide grains having a silver chloride content of 95 mole % or more are contained in a red-sensitive emulsion layer. More preferably the silver halide grains having a silver chloride content of 95 mole % or more are contained in a blue-sensitive emulsion layer, a green-sensitive emulsion layer and a red-sensitive emulsion layer.
The silver chloride content is preferably 96 mole % or more, and further preferably 97 mole % or more and less than 100 mole %.
In the light-sensitive material of the present invention, a silver bromide-rich phase is preferably provided to the silver halide grains having a silver chloride content of 95 mole % or more. Preferably the silver bromide-rich phase is prepared by epitaxially growing a localized phase having a silver bromide content of 10 mole % or more in terms of the content (percentage) of total silver bromide in the silver bromide-rich phase. The silver bromide content of the silver bromide-rich phase is preferably 10 mole % or more in total. However, if the silver bromide content is excessively high, the silver bromide-rich phase sometimes imparts unpreferable characteristics against the photographic light-sensitive material, such that when a pressure is applied to a light-sensitive material, desensitization occurs, and that sensitivity and/or gradation are substantially altered by fluctuation in the composition of a processing solution. Taking these points into consideration, the silver bromide content of the silver bromide-rich phase is preferably in the range of 10 mole % to 60 mole %, most preferably in the range of 20 mole % to 50 mole %. The silver bromide content of the silver bromide-rich phase can be analyzed according to X-ray diffraction method (for example, Shin-Jikken Kagaku Koza 6, Kozo Kaiseki (New Experimental Chemistry Course 6, Analysis of Structure), edited by Nihon kagaku kai, published by Maruzen), or the like. The silver bromide-rich phase is preferably composed of 0.1 mole % to 5 mole %, more preferably 0.3 mole % to 4 mole % of the total silver amount of the silver halide grains for use in the present invention.
The steps of preparing the silver halide emulsion for use in the present invention is composed of a silver halide grain-forming step utilizing a reaction between a water-soluble silver salt and a water-soluble halide, a desalting step, and a chemical ripening step, as generally well-known in the art. In present invention, the silver bromide-rich phase may be provided in any course of the foregoing steps. However, the silver bromide-rich phase is preferably provided after the desalting step, especially preferably after completion of the desalting step but before completion of chemical sensitization. It is preferred to incorporate complex ions of metal of the group VIII such as IrCl62xe2x88x92 in the silver bromide-rich phase. Further, when an iridium compound is incorporated in the silver bromide-rich phase of the silver halide emulsion grains, it is preferable that said rich phase is deposited together with at least 50 mole % of the total iridium to be added at the time of preparation of silver halide grains. It is more preferable that said rich phase is deposited together with at least 80 mole % of the total iridium to be added. It is most preferable that said rich phase is deposited together with the total iridium to be added. The phrase xe2x80x9csaid rich phase is deposited together with iridiumxe2x80x9d as used herein means that an iridium compound is supplied at the same time as a silver or halogen supply, just before a silver or halogen supply, or immediately after a silver or halogen supply, for formation of said rich phase. In the case where a silver bromide-rich phase is formed by mixing silver halide host grains and silver halide fine grains having a shorter average grain size and higher silver bromide content than those of said host grains, and thereafter ripening the resulting mixture, it is preferable that an iridium salt is previously incorporated in the silver halide fine grains having a high silver bromide content.
The silver halide grains for use in the present invention may be those having (100) planes, those having (111) planes, or those having both (100) planes and (111) planes, on an outer surface area, or they may contain higher dimensional planes. However, cube and tetradecahedron, each of which is mainly composed of (100) planes, are preferred. The size of the silver halide grains for use in the present invention may be in the range of the grain size usually employed in the art. However, the average grain size is preferably in the range of 0.1 xcexcm to 1.5 xcexcm. The grain size distribution may be a polydispersion or monodispersion. The latter is preferred. The variation coefficient of the grain size that indicates the degree of the monodispersion is preferably 0.2 or less, more preferably 0.15 or less, in terms of the ratio (s/d) of a statistical standard deviation (s) to an average grain size (d). Further, in order to provide a desired gradation, a blend of two or more of the foregoing monodisperse emulsions different in sensitivity preferably can be used in the same silver halide emulsion layer.
With respect to the shape of silver halide grains for use in the present invention, those having a regular crystal form, such as cubic or tetradecahedral as well as octahedral, an irregular crystal form, such as spherical, tabular, or the like, or a composite form of these forms, can be used. Further, grains having a mixture of these various crystal forms may also be used. It is preferred in the present invention that the proportion of the grains having such a regular crystal form as described above to the entire grains be 50% or more, preferably 70% or more, and more preferably 90% or more, in terms of wt %. Further, in addition to the grains having a regular crystal form, an emulsion in which the proportion of tabular grains having an average aspect ratio {the ratio of an equivalent circular diameter (which means a diameter of a circle equivalent to a grain""s projected area)/a grain thickness} of generally 5 or more, preferably 8 or more, to the entire grains is 50% by weight or more as a projected area can also be preferably used. The silver halide emulsion that is used in the present invention can be prepared according to the methods disclosed, for example, by P. Glafkides, in Chimie et Physique Photographique, Paul Montel (1967), by G. F. Duffin, in Photographic Emulsion Chemistry, Focal Press (1966), by V. L. Zelicman, et al., in Making and Coating Photographic Emulsion, Focal Press (1964), and the like. That is, any process, such as an acid process, a neutral process, and an ammoniacal process, can be used. Any of a single jet method, a double jet method, and a combination of them may be used as methods for reacting a soluble silver salt with a soluble halide. A method in which silver halide grains are formed in the atmosphere of excessive silver ion (a so-called reverse mixing method) can also be used. Further, a so-called controlled double jet method, which is one form of a double jet method, in which the pAg of the liquid phase in which the silver halide is formed is maintained constant, can also be used. According to this method, a silver halide emulsion having a regular crystal form and substantially a uniform grain size can be obtained.
Various compounds can be included in the silver halide emulsion for use in the present invention, to prevent fogging from occurring or stabilize photographic performances during manufacture, storage or photographic processing of the photographic material. That is, as a compound which can be added to the silver halide emulsion, there are many compounds known as an antifogging agent or stabilizer, such as azoles, for example, benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, and mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole and the like); mercaptopyrimidines, mercaptotriazines; thioketo compounds such as oxazolinethione; azaindenes, for example, triazaindenes, tetrazaindenes (particularly 4-hydroxy-substituted (1,3,3a,7)tetrazaindene), and pentazaindenes; benzenethiosulfonic acid, benzenesulfinic acid, and benzenesulfonamide. Mercaptotetrazoles are especially preferred. These compounds preferably act so that a high illumination intensity speed can be further enhanced, in addition to antifogging and stabilization.
As a hydrophilic binder which may be used in the silver halide color photographic light-sensitive material of the present invention, gelatin is generally used. However, as occasion demands, gelatin may be used in combination with any other hydrophilic colloid, such as other gelatin derivatives, graft copolymers of gelatin and other high molecules, proteins other than gelatin, sugar derivatives, cellulose derivatives, and synthetic hydrophilic high molecular materials such as homo- or copolymers.
The gelatin which is used in the silver halide color photographic light-sensitive material of the present invention may be a lime-processed gelatin, or an acid-processed gelatin. Further, it may be a gelatin manufactured by employing any one of a cattle bone, a cattle skin and a pig skin as a raw material. A lime-processed gelatin manufactured by employing the cattle bone or the pig skin as a raw material is preferred.
In the present invention, the total amount of a hydrophilic binder to be contained in light-sensitive silver halide emulsion layers and light-insensitive hydrophilic colloid layers extending from a support to the hydrophilic colloid layers furthest from the silver halide emulsion-coating side of the support, is preferably 8.0 g/m2 or less, most preferably from 7.0 g/m2 to 4.0 g/m2, from the viewpoint of a rapid processing. A small amount of a hydrophilic binder has an effect especially on advances in both color developing and washing speed.
In the present invention, the silver halide emulsion layer containing a yellow coupler may be arranged in any position on the support. For example, when silver halide tabular grains are used in the silver halide emulsion coating a yellow coupler, the layer containing a yellow coupler is coated preferably in a position more apart from the support than at least one layer of the magenta coupler-containing silver halide emulsion layer and the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of acceleration of color development, acceleration of silver removal, and reduction of a residual color by a sensitizing dye, the yellow coupler-containing silver halide emulsion layer is coated preferably in the most apart position from the support than the other silver halide emulsion layers. Further, from the viewpoint of a reduction in Blix discoloration, the cyan coupler-containing silver halide emulsion layer is preferably a middle layer between the other silver halide emulsion layers, and from the viewpoint of a reduction in light discoloration, the cyan coupler-containing silver halide emulsion layer is preferably the lowermost layer. Further, each color-forming layer of yellow, magenta or cyan may be composed of 2 or 3 layers. For example, it is preferable that a coupler layer not containing a silver halide emulsion is arranged to be adjacent to the silver halide emulsion layer, to form a color-forming layer, as described in JP-A-4-75055, JP-A-9-114035, JP-A-10xe2x88x92246940, U.S. Pat. No. 5,576,159, etc.
In the yellow coupler-containing silver halide emulsion layer, the amount of the hydrophilic binder is preferably 1.55 g/m2 or less, more preferably 1.45 g/m2 or less, most preferably 1.35 g/m2 or less but 0.60 g/m2 or more. Further, with respect to the thickness of the silver halide emulsion, the side length in the case where cubic grains are used is preferably 0.80 xcexcm or less, more preferably 0.75 xcexcm or less, most preferably 0.70 xcexcm or less but 0.30 xcexcm or more, and the side length in the case where tabular grains are used is preferably 0.40 xcexcm or less but 0.02 xcexcm or more, more preferably 0.30 xcexcm or less, further preferably 0.20 xcexcm or less, most preferably 0.15 xcexcm or less but 0.05 xcexcm or more. An aspect ratio of tabular grains is preferably 2 to 10, more preferably 3 to 8. A mixture of silver halide emulsions having different sizes and/or shapes is preferably used to control sensitivity, gradation and other photographic performance.
In the present invention, the amount of the silver halide emulsion to be coated is preferably 0.70 to 0.10 g/m2, more preferably 0.65 to 0.20 g/m2, most preferably 0.55 to 0.25 g/m2.
When cubic silver halide emulsion grains are used in the cyan-color-forming layer and the magenta-color-forming layer, the side length thereof is preferably 0.70 xcexcm or less, more preferably 0.50 xcexcm or less but 0.10 xcexcm or more.
In the present invention, the film thickness in the constitution of the photographic layer means the thickness, before processing, in the constitution of the photographic layer which is a layer over the support. Specifically, the film thickness can be obtained in any one of the following methods. In the first method, the film thickness can be obtained by cutting the silver halide color photographic light-sensitive material in a direction perpendicular to the support, and observing its cut surface under a microscope. The second method is a method of calculating the film thickness from the coating amount (g/m2) and specific gravity of each component in the constitution of the photographic layer.
For example, the specific gravity of typical gelatin for use in photography is 1.34 g/ml, and the specific gravity of silver halide is 5.59 g/ml, and other lipophilic additives are previously measured before coating, whereby the film thickness can be calculated in the second method.
In the present invention, the film thickness in the photographic layer constitution is preferably 10.0 xcexcm or less, more preferably 9.5 xcexcm or less, most preferably 9.0 xcexcm or less but 3.5 xcexcm or more.
In the present invention, the hydrophobic photographic material is an oil-soluble ingredient excluding the dye-forming coupler, and the oil-soluble ingredient is a lipophilic component remaining in the light-sensitive material after processing. Specific examples of the oil-soluble ingredient include the dye-forming coupler, a high-boiling organic solvent, a color-mixing inhibitor, an ultraviolet absorber, lipophilic additives, a lipophilic polymer or polymer latex, a matt agent, a slip (sliding) agent or the like, which are usually added as lipophilic fine-grains to the photographic constitutional layer. Accordingly, a water-soluble dye, a hardening agent, water-soluble additives and silver halide emulsions are not included in the oil-soluble ingredient. Further, a surfactant is usually employed in preparing lipophilic fine grains, and the surfactant is not regarded as the oil-soluble ingredient in the present invention.
The total amount of the oil-soluble ingredient in the present invention is preferably 5.5 g/m2 or less, further preferably 5.0 g/m2 or less, most preferably 4.5 g/m2 or less but 3.0 g/m2 or more. In the present invention, the value obtained by dividing the weight (g/m2) of the hydrophobic photographic material contained in the dye-forming coupler-containing layer by the weight (g/m2) of said dye-forming coupler, is preferably 4.5 or less, more preferably 3.5 or less, and most preferably 3.0 or less.
In the present invention, the ratio of the oil-soluble ingredient in the photographic layer constitution to the hydrophilic binder can be arbitrarily selected. The ratio thereof by weight in the photographic layer constitution other than the protective layer is preferably 0.05 to 1.50, more preferably 0.10 to 1.40. By optimizing the ratio of each layer, the film strength, abrasion resistance and curl characteristics can be regulated.
In the light-sensitive material according to the present invention, for the purpose of improving the sharpness or the like of images, dyes (particularly oxonol-type dyes), which can be decolored by processing, as described on pages 27 to 76 in European Patent Application No. 337,490A2, are preferably added to the hydrophilic colloidal layer such that the optical reflection density of the light-sensitive material at 680 nm becomes 0.50 or more, or 12 wt % or more (more preferably 14 wt % or more) of titanium oxide which is surface-treated with di- to tetra-hydric alcohols (e.g. trimethylol ethane) is preferably contained in a water-resistant resin layer of a support.
In the silver halide photographic light-sensitive material of the present invention, other conventionally known photographic materials and additives can be used.
For example, a transparent-type base or a reflective-type base can be used as the photographic base (support). As the transparent-type base, a transparent film, such as a cellulose nitrate film and a polyethylene terephthalate film; and one wherein a film, for example, of a polyester of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) or a polyester of NDCA, terephthalic acid, and EG, is provided with an information recording layer, such as a magnetic layer, are preferably used. As a reflective-type base, particularly, a reflective-type base, wherein a laminate has a plurality of polyethylene layers or polyester layers and wherein at least one of such water-resistant resin layers (laminated layers) contains a white pigment, such as titanium oxide, is preferable.
Further, the above water-resistant resin layers preferably contain a fluorescent whitening agent. Further, a fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the light-sensitive material. As the fluorescent whitening agent, preferably a benzoxazole-series fluorescent whitening agent, a cumarin-series fluorescent whitening agent, or a pyrazoline-series fluorescent whitening agent can be used, and more preferably a benzoxazolylnaphthalene-series fluorescent whitening agent or a benzoxazolylstilbene-series fluorescent whitening agent is used. The amount to be used is not particularly limited, but preferably it is 1 to 100 mg/m2. When it is mixed with a water-resistant resin, preferably the mixing proportion is 0.0005 to 3% by weight, and more preferably 0.001 to 0.5% by weight, to the resin.
The reflective-type base may be one wherein a hydrophilic colloid layer containing a white pigment is applied on a transparent-type base or a reflective-type base described in the above.
Further, the reflective-type base may be a base having a specular reflective- or a second-type diffusion reflective metal surface.
For the above reflective-type base, silver halide emulsions, as well as different metal ion species to be doped into silver halide grains, antifoggants or storage stabilizers of silver halide emulsions, chemical sensitizing methods (sensitizers) and spectrally sensitizing methods (spectral sensitizers) for silver halide emulsions, cyan, magenta, and yellow couplers and methods for emulsifying and dispersing them, dye-image-preservability improving agents (antistaining agents and anti-fading agents), dyes (colored layers), gelatins, layer structures of light-sensitive materials, the pH of coatings of light-sensitive materials, and the like, those described in the patents shown in Tables 1 and 2 can be preferably applied in the present invention.
As the cyan, magenta, and yellow couplers additionally used in the present invention, further, couplers described, for example, in JP-A-62-215272, page 91, right upper column, line 4 to page 121, left upper column, line 6; JP-A-2-33144, page 3, right upper column, line 14 to page 18, left upper column, the last line, and page 30, right upper column, line 6 to page 35, right lower column, line 11; and EP-A-0 355 660 (A2), page 4, line 15 to line 27, page 5, line 30 to page 28, the last line, page 45, line 29 to line 31, and page 47, line 23 to page 63, line 50, JP-A-8-122984, and JP-A-9-222704 are also useful. Further, as the cyan coupler, pyrazolotriazole couplers are preferably used. Among these couplers especially preferred are those represented by formula (I) or (II) in JP-A-5-313324 and those represented by formula (I) in JP-A-6-347960 and exemplified couplers described in these patent publications.
In the present invention, known color-mixing preventing agents may be used. Among the agents, those described in the following patent publications are preferable.
For example, high molecular weight redox compounds described in JP-A-5-333501, phenidone- or hydrazine-series compounds described in Japanese patent application No. 9-140719 and U.S. Pat. No. 4,923,787, and white couplers described in JP-A-5-249637, JP-A-10xe2x88x92282615 and German Patent No.19629142A1 may be used. In order to raise the pH of a developing solution and to promote developing rate in particular, it is preferable to use redox compounds described, for example, in German Patent Nos.19618786A1 and 19806846A1, EP Patent Nos.839623A1 and 842975A1, and France Patent No.2760460A1.
In the present invention, an ultraviolet light absorber having high molar extinction coefficient is preferably used as a ultraviolet light absorber. For example, as these compounds, compounds containing a triazine skeleton may be used. Compounds described, for example, in JP-A-46-3335, JP-A-55-152776, JP-A-5-197074, JP-A-5-232630, JP-A-5-307232, JP-A-6-211813, JP-A-8-53427, JP-A-8-234364, JP-A-8-239368, JP-A-9-31067, JP-A-10-115898, JP-A-10-147577, JP-A-10-182621, JP-T-8-501291 (xe2x80x9cJP-Txe2x80x9d means published searched patent publication), European Patent No. 711804A, and German Patent No. 19739797A, is preferable.
As fungiproofing/mildewproofing agents that can be used in the present invention, those described in JP-A-63-271247 are useful. As a hydrophilic colloid used in photographic layers that constitute the light-sensitive material, gelatin is preferable, and in particular, preferably heavy metals contained as impurities, such as iron, copper, zinc, and manganese are 5 ppm or less and more preferably 3 ppm or less.
Also, preferably calcium content in the light-sensitive material is 20 mg/m2 or less, more preferably 10 mg/m2 or less, most preferably 5 mg/m2 or less.
The light-sensitive material of the present invention is for use in not only printing systems that use usual negative printers, it is also suitable for scanning exposure systems using cathode rays (CRT).
In comparison with apparatuses using lasers, cathode ray tube exposure apparatuses are simple and compact and make the cost low. Further, the adjustment of optical axes and colors is easy.
For the cathode ray tubes used for image exposure, use is made of various emitters that emit light in spectral regions as required. For example, any one of, or a mixture of two or more of, a red emitter, a green emitter, and a blue emitter may be used. In particular, a cathode ray tube that emits white light by mixing these phosphors is often used.
When the cathode ray tube has phosphors that show light emission in multiple spectral regions, multiple colors may be exposed at a time; namely, image signals of multiple colors are inputted into the cathode ray tube, to emit lights from the tube surface. A method in which exposure is made in such a manner that image signals for respective colors are inputted successively, to emit the respective colors successively, and they are passed through films for cutting out other colors (surface-successive exposure), may be employed, and generally the surface-successive exposure is preferred to make image quality high, since a high-resolution cathode ray tube can be used.
The light-sensitive material of the present invention is preferably used for digital scanning exposure system that uses monochromatic high-density light, such as a second harmonic generating light source (SHG) that comprises a combination of a nonlinear optical crystal with a semiconductor laser or a solid state laser using a semiconductor laser as an excitation light source, a gas laser, a light-emitting diode, or a semiconductor laser. To make the system compact and inexpensive, it is preferable to use a semiconductor laser or a second harmonic generating light source (SHG) that comprises a combination of a nonlinear optical crystal with a semiconductor laser or a solid state laser. Particularly, to design an apparatus that is compact, inexpensive, long in life, and high in stability, the use of a semiconductor laser is preferable, and it is preferable to use a semiconductor laser for at least one of the exposure light sources.
In an SHG light source obtained by combining a nonlinear optical crystal with a semiconductor laser or a solid state laser that uses a semiconductor laser as an excitation light source, since the emitting wavelength of the laser can be halved, blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be present in each of the usual three wavelength regions, the blue region, the green region and the red region, to obtain an image.
If the exposure time in this scanning exposure is defined as the time for which a picture element size is exposed to light with the density of the picture element being 400 dpi, preferably the exposure time is 10xe2x88x924 sec or less, more preferably 10xe2x88x926 sec or less.
Preferable scanning exposure systems that can be applied to the present invention are described in detail in the patents listed in the above Table.
Further, in order to process the light-sensitive material of the present invention, processing materials and processing methods described in JP-A-2-207250, page 26, right lower column, line 1, to page 34, right upper column, line 9, and in JP-A-4-97355, page 5, left upper column, line 17, to page 18, right lower column, line 20, can be preferably applied. Further, as the preservative used for this developing solution, compounds described in the patents listed in the above Table are preferably used.
As the systems for conducting development of the light-sensitive material of the present invention after the exposure thereof, a wet system, such as the conventional method, in which development is carried out by using a developing solution containing an alkali agent and a developing agent, and a method in which a developing agent is built in the light-sensitive material and the development is carried out by using an activator solution, such as an alkali solution free from any developing agent, as well as a heat development system that does not use a processing solution, can be used. Particularly, since the activator method does not contain a developing agent in the processing solution, the control and the handling of the processing solution are easy, and the load at the time of waste liquor treatment is less, which makes the activator method preferable in view of environmental conservation.
In the activator method, as the developing agent or its precursor to be built in the light-sensitive material, for example, hydrazine-type compounds described in JP-A-8-234388, JP-A-9-152686, JP-A-9-152693, JP-A-9-211814, and JP-A-9-160193 are preferable.
Further, a development method in which the coated amount of silver in the light-sensitive material is decreased, and an image intensification processing (intensification processing) is carried out using hydrogen peroxide, is also preferably used. Particularly, it is preferable to use this method for the activator method. Specifically, preferably use is made of image-forming methods described in JP-A-8-297354 and JP-A-9-152695, wherein an activator solution containing hydrogen peroxide is used.
In the activator method, after the processing with an activator solution, a desilvering process is generally carried out, but in the image intensifying process in which a light-sensitive material with the amount of silver lowered is used, the desilvering process can be omitted, and a simple process, such as a washing process or a stabilizing process, can be carried out. Further, in a system in which image information is read from a light-sensitive material by a scanner or the like, a processing mode without requiring a desilvering process can be employed, even when a light-sensitive material having a large amount of silver, such as a light-sensitive material for shooting (photographing), is used.
As the processing materials and processing methods for the activator solution, the desilvering solution (bleach/fix solution), the washing water and the stabilizing solution that are used in the processing of the light-sensitive material of the present invention, known ones can be used. Preferably, those described in Research Disclosure Item 36544 (September 1994), pages 536 to 541, and JP-A-8-234388, can be used.
In the processing of the light-sensitive material of the present invention, the term xe2x80x9ccolor-developing timexe2x80x9d means a period of time required from the beginning of dipping of a light-sensitive material into a color developing solution until the light-sensitive material is dipped into a blix solution in the subsequent processing step. In the case where a processing is carried out using, for example, an autoprocessor, the color developing time is the sum total of a time in which a light-sensitive material has been dipped in a color developing solution (so-called xe2x80x9ctime in the solutionxe2x80x9d) and a time in which the light-sensitive material after departure from the color developing solution has been conveyed in the air toward a bleach-fixing bath in the step subsequent to color development (so-called xe2x80x9ctime in the airxe2x80x9d). Similarly the term xe2x80x9cbleach-fixing timexe2x80x9d means a period of time required from the beginning of dipping of a light-sensitive material into a bleach-fixing solution until the light-sensitive material is dipped into a washing or stabilizing bath in the subsequent processing step. Further, the term xe2x80x9cwashing or stabilizing timexe2x80x9d means a period of time in which a light-sensitive material is staying in the washing or stabilizing solution until it begins to be conveyed toward a drying step (so-called xe2x80x9ctime in the solutionxe2x80x9d).
The light-sensitive material of the present invention is preferably processed by rapid processing, and the color developing time is preferably 60 seconds or less, more preferably in the range of 50 seconds to 6 seconds. Similarly the bleach-fixing time is preferably 60 seconds or less, more preferably in the range of 50 seconds to 6 seconds. Further, the washing or stabilizing time is preferably 150 seconds or less, more preferably in the range of 130 seconds to 6 seconds.
As a drying method among the processing steps for the light-sensitive material of the present invention, any one of the methods which are conventionally known to dry color photographic light-sensitive materials rapidly may be adopted. From the object of the present invention, it is preferable to dry a color photographic light-sensitive material within 20 sec, more preferably within 15 sec, and most preferably in 5 sec to 10 sec.
As the drying system, any one of a contact heating system and a hot air-blowing system may be used, and a structure of a combination of the contact heating system and the hot air-blowing system makes it possible to carry out drying more rapidly than the above independent system, and the combination is hence preferable. In a more preferred embodiment concerning the drying method according to the present invention, the light-sensitive material is contact-heated using a heat-roller and then blow-dried using hot air blown toward the light-sensitive material from a perforated panel or nozzles. It is preferable that, in the blow-drying section, the mass velocity of the hot air blown per heat-receiving unit area of the light-sensitive material be 1000 kg/m2xe2x80xa2hr or more. The diffuser (outlet of blown air) has preferably a shape reduced in pressure loss and examples of the shape are given in FIG. 7 to FIG. 15 described in JP-A-9-33998.
The silver halide color photographic light-sensitive material of the present invention provides the following excellent effects. Namely, the light-sensitive material is excellent in both a rapid processing suitability and a representation of the shading at the high density portion of the image obtained by a scanning exposure. In addition, a high quality of a color photographic image is also formed by a conventional surface exposure.
The silver halide color photographic light-sensitive material of the present invention provides an excellent effect on that a rapid processing suitability is excellent; the change in color balance at the peripheral portion of a color photograph obtained by a scanning exposure is restrained and a high maximum colored density is obtained by the scanning exposure; and in addition a high quality of a color photographic image is also formed by a conventional surface exposure.
The present invention will be described in more detail with reference to the following examples, but the present invention is not restricted to them.